US5169428A - Tetrahydrophthalimide derivative and herbicide composition containing same - Google Patents
Tetrahydrophthalimide derivative and herbicide composition containing same Download PDFInfo
- Publication number
- US5169428A US5169428A US07/726,724 US72672491A US5169428A US 5169428 A US5169428 A US 5169428A US 72672491 A US72672491 A US 72672491A US 5169428 A US5169428 A US 5169428A
- Authority
- US
- United States
- Prior art keywords
- compound
- tetrahydrophthalimide
- methyl
- hydrogen
- derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/32—Cyclic imides of polybasic carboxylic acids or thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/46—N-acyl derivatives
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
Definitions
- This invention relates to a novel tetrahydrophthalimide derivative which has excellent herbicidal activity and selectivity.
- the herbicidal activity of the tetrahydrophthalimide derivatives is well-known in the art.
- Japanese Patent Disclosure (Kokai) Nos. 163365/82 and 110566/83 disclose the tetrahydrophthalimide derivatives having herbicidal activity, which are represented by the formula [A] and [B], respectively.
- the known tetrahydrophthalimide derivatives do not have satisfactory herbicidal activity.
- the other known tetrahydrophthalimide derivatives do not have satisfactory selectivity. That is, when the herbicide comprising the derivative is applied to the crops and weeds, not only the weeds, but also the crops may be damaged. Thus, the safety of the herbicide is not good.
- the object of the present invention is to provide a novel tetrahydrophthalimide derivative which has a high herbicidal activity and selectivity.
- Another object of the present invention is to provide a herbicide composition having a high herbicidal activity and selectivity.
- the present inventors intensively studied to find that a specific tetrahydrophthalimide derivative has a high herbicidal activity and selectivity to complete the present invention.
- the present invention provides a novel tetrahydrophthalimide derivative of the formula [I]: ##STR6## wherein X 1 and X 2 , the same or different, represent halogen, hydrogen or trifluoromethyl; R represents ##STR7## (wherein R 1 and R 2 , the same or different, represent hydrogen or methyl, R 3 represents 2-tetrahydrofurfuryl or 3-methyl-1,2,4-oxadiazole-5-yl), ##STR8## (wherein R 4 is hydrogen or methyl, R 5 is methyl or benzyl), ##STR9## (wherein R 6 represents hydrogen or methyl, R 7 is halogen or C 1 -C 4 alkyl), (wherein R 8 is hydrogen, acyl or arylalkyl), cyano, or --CH 2 OR 9 (wherein R 9 is hydrogen, acetyl, halophenyl, C 1 -C 4 alkyl which may be substituted with alkoxycarbonyl).
- the present invention a novel tetrahydrophthalimide derivative with high herbicidal activity and selectivity was provided As will be clearly demonstrated in the Examples later described, the tetrahydrophthalimide derivative of the present invention has a high herbicidal activity while it does not substantially damage the useful crops such as wheat, corn and soybean. Thus, it can be used safely for the inhibition of the growth of weeds in the field of such crops.
- Preferred examples of the tetrahydrophthalimide derivative of the present invention represented by the formula [I] above include those represented by the following formula [II]: ##STR10##wherein R 1 and R 2 , the same or different, represent hydrogen or methyl, R 3 represents 2-tetrahydrofurfuryl or 3-methyl-1,2,4-oxadiazol-5-yl.
- Second group of the preferred examples of the tetrahydrophthalimide derivative of the present invention represented by the formula [I] includethose represented by the following formula [III]: ##STR15##wherein R 4 is hydrogen or methyl, R 5 is methyl or benzyl.
- Third group of the preferred examples of the tetrahydrophthalimide derivative of the present invention represented by the formula [I] includethose represented by the following formula [IV]: ##STR18##wherein X 3 and X 4 , the same or different, represent halogen, R 6 represents hydrogen or methyl, R 7 represents halogen or C 1 -C 4 alkyl.
- tetrahydrophthalimide derivative of the present invention is represented by the following formula [V]: ##STR19##wherein X 3 and X 4 , the same or different, represent halogen, R 8 represents hydrogen, acyl or arylalkyl.
- tetrahydrophthalimide derivative of the present invention is represented by the following formula [VI]: ##STR22##wherein X 1 and X 2 , the same or different, represent hydrogen, halogen or trifluoromethyl, R 10 represents cyano or --CH 2 OR 9 (wherein R 9 represents hydrogen, acetyl, halophenyl, C 1 -C 4 alkyl which may be substituted with alkoxycarbonyl).
- the tetrahydrophthalimide derivative of the present invention may be prepared by various processes. More particularly, those represented by theformula [II] may be prepared according to the following Equation 1: ##STR25##
- Hal represents halogen (Hal means halogen also in the subsequent formulae)
- R 1 , R 2 and R 3 represent the same meaning as in formula [II].
- the reaction may be conducted in an appropriate solvent under the presence of a base at a temperature ranging from 0° C.-150° C., preferably 20°-100° C. for several minutes to 48 hours.
- Preferred examples of the solvents which may be employed in the reaction may include ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and xylene; ethers such as ethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as chlorobenzene, chloroform, tetrachloromethane and dichloroethane; tertiaryamines such as triethylamine, pyridine and dimethylaniline; and polar solvents such as acetonitrile, dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide.
- ketones such as acetone and methyl ethyl ketone
- aromatic hydrocarbons such as benzene and xylene
- ethers such as ethyl ether, tetrahydrofuran and dioxane
- halogenated hydrocarbons such as chloro
- the bases which may be employed in the reaction may include organic bases such as triethylamines, 1,3-diazabicyclo[5,4,0]undec-7-ene and dimethylaniline; alkali metal hydroxide such as sodium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkaline metal salts of carbonic acid such as sodiumcarbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; and metal hydrides such as sodium hydride.
- organic bases such as triethylamines, 1,3-diazabicyclo[5,4,0]undec-7-ene and dimethylaniline
- alkali metal hydroxide such as sodium hydroxide
- alkaline earth metal hydroxides such as calcium hydroxide
- alkaline metal salts of carbonic acid such as sodiumcarbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate
- metal hydrides such as sodium hydride.
- tetrahydrophthalimide derivatives represented by the formula [III] may be prepared according to the following Equation 2 or 3: ##STR26##
- the reaction may be conducted in the same conditions as in Equation 1.
- the solvents and bases which are preferred in Equation 1 are also preferred inthese reactions.
- tetrahydrophthalimide derivatives represented by the formula [IV] may be prepared according to the following Equation 4 or 5: ##STR27##
- the reaction may be conducted in the same conditions as in Equation 1.
- the solvents and bases which are preferred in Equation 1 are also preferred inthese reactions.
- tetrahydrophthalimide derivatives represented by the formula [V] may beprepared according to the following Equation 6: ##STR28##
- the reaction may be conducted in the same conditions as in Equation 1.
- the solvents and bases which are preferred in Equation 1 are also preferred inthese reactions.
- tetrahydrophthalimide derivatives represented by the formula [VI] may be prepared according to the following Equation 7 or 8: ##STR29##
- the reaction according to the Equation 7 may be conducted in the same conditions as in Equation 1.
- the solvents and bases which are preferred inEquation 1 are also preferred in these reactions.
- the reaction according to the Equation 8 may be conducted in the presence or absence of a solvent, in the presence of a catalyst, at a temperature ranging from -20° C. to 300° C., preferably 0° C.-200° C. for several minutes to 48 hours.
- Preferred examples of the catalysts which may be employed in the reaction of Equation 8 may include chlorinating agents or dehydrants such as phosphorus oxychloride, phosphorus pentoxide, phosphorus pentachloride, phosphorus trichloride and sulfuryl chloride; dehydrating reagents such astriethylamine, chloroformate, DCC and anhydrous acetic acid.
- chlorinating agents or dehydrants such as phosphorus oxychloride, phosphorus pentoxide, phosphorus pentachloride, phosphorus trichloride and sulfuryl chloride
- dehydrating reagents such astriethylamine, chloroformate, DCC and anhydrous acetic acid.
- the amount of the catalyst is usually 1 to 100 equivalents with respect to 1 equivalent of the compound [XXI].
- the present invention further provides a herbicide composition comprising the tetrahydrophthalimide derivative of the present invention as effectiveingredient in an agriculturally acceptable carrier.
- the herbicide composition of the present invention is effective for inhibiting the growth of various weeds growing in paddy field including the weeds belonging to the Gramineae such as barnyardgrass; broadleaved weeds such as Falsepinpernel, spindle-flowered rotala, water starwart and monochoria;and those belonging to the family cyperaceae such as small flower umbrellaplant, slender spikerush and water nutgrass.
- the tetrahydrophthalimide derivative of the present invention is particularly effective for inhibiting the growth of weeds growing in fields, such as mustard, virginia pepperweed, catchweed badstraw, Kinutaso (Galium kinuta), chick weed, Common lambsquaters, nottle (Utrica Thunbergiana), Common groundsel, Alender amaranth, Cocklebur, Pale smartweed, Velvetleaf and barynard grass.
- the herbicide composition of the present invention does not substantially damage the crops belonging to Family Graminae such as corn, rice and wheat, so that it is highly safe.
- liquid carrier or solid carrier may be employed.
- liquid carrier ordiluent may include water, hydrocarbons, ethers, alkoxy alcohols, ketones, esters, amides and sulfoxides.
- Preferred examples of the solid carriers orextender may include powder and granules of inorganic materials such as slaked lime, gypsum, calcium carbonate, silica, pearlite, pumice, diatomaceous earth, alumina, zeolite and clay minerals (e.g., talc, vermiculite and kaolinite); powder and granules of plant products such as starch, cereals and glucose; and powder and granules of synthetic productssuch as phenol resins, carbon resins and vinyl chloride resins.
- the concentration of the active ingredient in the composition is not critical and may usually be 0.1% by weight to 90% by weight, preferably 1% by weight to 80% by weight.
- the herbicide composition of the present invention may contain a surfactant.
- the surfactants are well-known and widely used in the art.
- Preferred examples of the surfactants include anion surfactants such as alkylsulfate esters, arylsulfonic acids, salts of succinic acid and polyethyleneglycolalkylaryl ethers and ester salts of sulfuric acid; cation surfactants such as alkylamines and polyoxyethylenealkylamines; non-ionic surfactants such as polyoxyethyleneglycol ethers and polyol esters; and ampholytic surfactants.
- the herbicide composition of the present invention may contain other additives which are often employed in herbicide compositions.
- the examples of such additives may include stabilizers, dispersion stabilizers, fixing agents, effect prolongers and synergists.
- the composition may also contain other herbicides, bacteriocides, fungicides and the like.
- the herbicide composition may be formulated to an emulsifiable concentrate,wettable powder, aqueous solution, oily solution, granule or powder.
- the methods of formulating herbicide composition are well-known in the art.
- This formulation may be prepared by uniformly mixing the components.
- This composition may be prepared by mixing and pulverizing the components.
- This composition may be prepared by mixing and pulverizing the components.
- the amount of the compound of the present invention to be applied to the field varies depending on the formulation of the composition, method of application, species and stage of growth of the weeds. Typically, the amount to be applied may be 0.05 kg/ha to 10 kg/ha, preferably 0.1 kg/ha to 5 kg/ha in terms of the weight of the active compound of the present invention.
- the herbicide composition of the present invention may directly be applied to the leaves or stems of weeds or to the field before the germination of the weeds.
- the herbicide composition may be applied as it is or may be diluted with water before use.
- Example 1 The same operation as in Example 1 was repeated except that a halogen compound [VIII]](see Equation 1) having methyl groups as R 1 and R 2 , and 3-methyl-1,2,4-oxadiazol-5-yl group as R 3 was used to obtain the Compound No. 1.
- a halogen compound [VIII]] (see Equation 1) having methyl groups as R 1 and R 2 , and 3-methyl-1,2,4-oxadiazol-5-yl group as R 3 was used to obtain the Compound No. 1.
- Example 2 The same operation as in Example 1 was repeated except that a halogen compound [VIII] (see Equation 1) having hydrogen as R 1 and methyl group as R 2 , and 3-methyl-1,2,4-oxadiazol-5-yl group as R 3 was used to obtain the Compound No. 2.
- a halogen compound [VIII] (see Equation 1) having hydrogen as R 1 and methyl group as R 2 , and 3-methyl-1,2,4-oxadiazol-5-yl group as R 3 was used to obtain the Compound No. 2.
- Example 1 The same operation as in Example 1 was repeated except that a halogen compound [VIII] (see Equation 1) having hydrogen as R 1 and R 2 , and 3-methyl-1,2,4-oxadiazol-5-yl group as R 3 was used to obtain the Compound No. 4.
- a halogen compound [VIII] (see Equation 1) having hydrogen as R 1 and R 2 , and 3-methyl-1,2,4-oxadiazol-5-yl group as R 3 was used to obtain the Compound No. 4.
- Example 5 The same procedure as in Example 5 was repeated except that the compounds tested were Compound Nos. 5-7. Further, for comparison, 5-[2-chloro-4-trifluoromethyl-phenoxy]-2-nitro-benzoic acid (Comparative Compound C) and the Comparative Compound A described in Example 5 were also tested. The results are shown in Table 7 below.
- Example 9 The same procedure as in Example 5 was repeated except that the compounds tested were Compound Nos. 11-18. Further, for comparison, the Comparative Compound D described in Example 21 was also tested. The results are shown in Table 9 below.
- Example 21 The same procedure as in Example 21 was repeated except that the compounds tested were Compound No.s 19-23. For comparison, the Comparative Compound D described in Example 21 was also tested. The results are shown in Table 10 below.
- Example 5 The same procedure as in Example 5 was repeated except that the compounds tested were Compound Nos. 19-23. Further, for comparison, the Comparative Compound D described in Example 21 was also tested. The results are shown in Table 11 below.
- Example 31 The same procedure as in Example 31 was repeated except that N-(4-trifluoromethyl-5-aminocarbonylphenyl)-3,4,5,6-tetrahydrophthalimide was used to obtain the Compound No. 31.
- Example 21 The same procedure as in Example 21 was repeated except that the compounds tested were Compound Nos. 24-30.
- the Comparative Compound A described in Example 5 was also tested. The results are shown in Table 12 below.
- Example 5 The same procedure as in Example 5 was repeated except that the compounds tested were Compound Nos. 24, 25, 27-31. Further, for comparison, the Comparative Compound A described in Example 5 was also tested. The resultsare shown in Table 13 below.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Disclosed is a tetrahydrophthalimide derivative of the formula (I): <IMAGE> [I] wherein X1 and X2, the same or different, represent halogen, hydrogen or trifluoromethyl; R represents <IMAGE> (wherein R1 and R2, the same or different, represent hydrogen or methyl, R3 represents 2-tetrahydrofurfuryl or 3-methyl-1,2,4-oxadiazol-5-yl), <IMAGE> (wherein R4 is hydrogen or methyl, R5 is methyl or benzyl), <IMAGE> (wherein R6 represents hydrogen or methyl, R7 is halogen or C1 -C4 alkyl), <IMAGE> (wherein R8 is hydrogen, acyl or arylalkyl), cyano, or -CH2OR9 (wherein R9 is hydrogen, acetyl, halophenyl, C1-C4 tetrahydrophthalimide derivative of the present invention is useful as a herbicide.
Description
This is a continuation of application Ser. No. 07/291,759, filed Dec. 29, 1988, now abandoned.
I. Field of the Invention
This invention relates to a novel tetrahydrophthalimide derivative which has excellent herbicidal activity and selectivity.
II. Description of the Related Art
The herbicidal activity of the tetrahydrophthalimide derivatives is well-known in the art. For example, Japanese Patent Disclosure (Kokai) Nos. 163365/82 and 110566/83 disclose the tetrahydrophthalimide derivatives having herbicidal activity, which are represented by the formula [A] and [B], respectively.
However, some of the known tetrahydrophthalimide derivatives do not have satisfactory herbicidal activity. The other known tetrahydrophthalimide derivatives do not have satisfactory selectivity. That is, when the herbicide comprising the derivative is applied to the crops and weeds, not only the weeds, but also the crops may be damaged. Thus, the safety of the herbicide is not good.
Accordingly, the object of the present invention is to provide a novel tetrahydrophthalimide derivative which has a high herbicidal activity and selectivity.
Another object of the present invention is to provide a herbicide composition having a high herbicidal activity and selectivity.
The present inventors intensively studied to find that a specific tetrahydrophthalimide derivative has a high herbicidal activity and selectivity to complete the present invention.
That is, the present invention provides a novel tetrahydrophthalimide derivative of the formula [I]: ##STR6## wherein X1 and X2, the same or different, represent halogen, hydrogen or trifluoromethyl; R represents ##STR7## (wherein R1 and R2, the same or different, represent hydrogen or methyl, R3 represents 2-tetrahydrofurfuryl or 3-methyl-1,2,4-oxadiazole-5-yl), ##STR8## (wherein R4 is hydrogen or methyl, R5 is methyl or benzyl), ##STR9## (wherein R6 represents hydrogen or methyl, R7 is halogen or C1 -C4 alkyl), (wherein R8 is hydrogen, acyl or arylalkyl), cyano, or --CH2 OR9 (wherein R9 is hydrogen, acetyl, halophenyl, C1 -C4 alkyl which may be substituted with alkoxycarbonyl).
By the present invention, a novel tetrahydrophthalimide derivative with high herbicidal activity and selectivity was provided As will be clearly demonstrated in the Examples later described, the tetrahydrophthalimide derivative of the present invention has a high herbicidal activity while it does not substantially damage the useful crops such as wheat, corn and soybean. Thus, it can be used safely for the inhibition of the growth of weeds in the field of such crops.
Preferred examples of the tetrahydrophthalimide derivative of the present invention represented by the formula [I] above include those represented by the following formula [II]: ##STR10##wherein R1 and R2, the same or different, represent hydrogen or methyl, R3 represents 2-tetrahydrofurfuryl or 3-methyl-1,2,4-oxadiazol-5-yl.
Preferred and non-limiting specific examples of the tetrahydrophthalimide derivative represented by the formula [II]include those summarized in Table 1 below.
TABLE 1
______________________________________
Compound No. R.sup.1 R.sup.2 R.sup.3
______________________________________
1 CH.sub.3 CH.sub.3
##STR11##
2 H CH.sub.3
##STR12##
3 CH.sub.3 H
##STR13##
4 H H
##STR14##
______________________________________
Second group of the preferred examples of the tetrahydrophthalimide derivative of the present invention represented by the formula [I] includethose represented by the following formula [III]: ##STR15##wherein R4 is hydrogen or methyl, R5 is methyl or benzyl.
Preferred and non-limiting specific examples represented by the formula [III]include those summarized in Table 2 below.
TABLE 2
______________________________________
Compound No. R.sup.4 R.sup.5
______________________________________
5 CH.sub.3 CH.sub.3
6 H
##STR16##
7 CH.sub.3
##STR17##
______________________________________
Third group of the preferred examples of the tetrahydrophthalimide derivative of the present invention represented by the formula [I] includethose represented by the following formula [IV]: ##STR18##wherein X3 and X4, the same or different, represent halogen, R6 represents hydrogen or methyl, R7 represents halogen or C1 -C4 alkyl.
Preferred and non-limiting specific examples represented by the formula [IV]include those summarized in Table 3 below.
TABLE 3
______________________________________
Compound No. R.sup.6 X.sup.3
X.sup.4 R.sup.7
______________________________________
8 H H Cl --
9 H H Cl 2-F
10 H H Cl 4-F
11 H F Cl --
12 H F Cl 2-F
13 H F Cl 2-CH.sub.3
14 H Cl Cl 2-F
15 H Br Cl --
16 H Br Cl 2-F
17 CH.sub.3 F Cl --
18 CH.sub.3 Cl Cl --
______________________________________
Fourth group of preferred examples of the tetrahydrophthalimide derivative of the present invention is represented by the following formula [V]: ##STR19##wherein X3 and X4, the same or different, represent halogen, R8 represents hydrogen, acyl or arylalkyl.
Preferred and non-limiting specific examples of those represented by the formula [V] include those summarized in Table 4 below.
TABLE 4
______________________________________
Compound No. X.sup.3
X.sup.4 R.sup.8
______________________________________
19 F Cl H
20 F Cl COCH.sub.3
21 F Cl
##STR20##
22 Cl Cl
##STR21##
23 Cl Cl H
______________________________________
Fifth group of preferred examples of the tetrahydrophthalimide derivative of the present invention is represented by the following formula [VI]: ##STR22##wherein X1 and X2, the same or different, represent hydrogen, halogen or trifluoromethyl, R10 represents cyano or --CH2 OR9 (wherein R9 represents hydrogen, acetyl, halophenyl, C1 -C4 alkyl which may be substituted with alkoxycarbonyl).
Preferred and non-limiting specific examples of those represented by the formula [VI] are summarized in Table 5 below.
TABLE 5
______________________________________
Compound No. X.sup.1 X.sup.2 R.sup.8
______________________________________
24 H Cl CH.sub.2 OH
25 H Cl CH.sub.2 OCOCH.sub.3
26 H Cl
##STR23##
27 H Cl
##STR24##
28 H Cl CN
29 H Br CN
30 F Cl CN
31 H CF.sub.3
CN
______________________________________
The tetrahydrophthalimide derivative of the present invention may be prepared by various processes. More particularly, those represented by theformula [II] may be prepared according to the following Equation 1: ##STR25##
In the above Equation 1, Hal represents halogen (Hal means halogen also in the subsequent formulae), R1, R2 and R3 represent the same meaning as in formula [II].
The reaction may be conducted in an appropriate solvent under the presence of a base at a temperature ranging from 0° C.-150° C., preferably 20°-100° C. for several minutes to 48 hours.
Preferred examples of the solvents which may be employed in the reaction may include ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and xylene; ethers such as ethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as chlorobenzene, chloroform, tetrachloromethane and dichloroethane; tertiaryamines such as triethylamine, pyridine and dimethylaniline; and polar solvents such as acetonitrile, dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide.
Preferred examples of the bases which may be employed in the reaction may include organic bases such as triethylamines, 1,3-diazabicyclo[5,4,0]undec-7-ene and dimethylaniline; alkali metal hydroxide such as sodium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkaline metal salts of carbonic acid such as sodiumcarbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; and metal hydrides such as sodium hydride.
Typically, 1-5 equivalents of the halogen compound [VIII] and 1-10 equivalents of the base are reacted with 1 equivalent of the compound [VII].
The tetrahydrophthalimide derivatives represented by the formula [III] may be prepared according to the following Equation 2 or 3: ##STR26##
The reaction may be conducted in the same conditions as in Equation 1. The solvents and bases which are preferred in Equation 1 are also preferred inthese reactions.
Typically, 1-5 equivalents of the compound [X] or [XII] and 1-10 equivalents of the base are reacted with 1 equivalent of the compound [IX]or [XI].
The tetrahydrophthalimide derivatives represented by the formula [IV] may be prepared according to the following Equation 4 or 5: ##STR27##
The reaction may be conducted in the same conditions as in Equation 1. The solvents and bases which are preferred in Equation 1 are also preferred inthese reactions.
Typically, 1-5 equivalents of the compound [XIV] or [XVI] and 1-10 equivalents of the base are reacted with 1 equivalent of the compound [XIII] or [XV].
The tetrahydrophthalimide derivatives represented by the formula [V] may beprepared according to the following Equation 6: ##STR28##
The reaction may be conducted in the same conditions as in Equation 1. The solvents and bases which are preferred in Equation 1 are also preferred inthese reactions.
Typically, 1-5 equivalents of the compound [XVIII] and 1-10 equivalents of the base are reacted with 1 equivalent of the compound [XVII].
The tetrahydrophthalimide derivatives represented by the formula [VI] may be prepared according to the following Equation 7 or 8: ##STR29##
The reaction according to the Equation 7 may be conducted in the same conditions as in Equation 1. The solvents and bases which are preferred inEquation 1 are also preferred in these reactions.
Typically, 1-5 equivalents of the compound [XX] and 1-10 equivalents of thebase are reacted with 1 equivalent of the compound [XIX].
The reaction according to the Equation 8 may be conducted in the presence or absence of a solvent, in the presence of a catalyst, at a temperature ranging from -20° C. to 300° C., preferably 0° C.-200° C. for several minutes to 48 hours.
The solvents preferred in the reaction of Equation 1 are also preferred in the reaction of Equation 8.
Preferred examples of the catalysts which may be employed in the reaction of Equation 8 may include chlorinating agents or dehydrants such as phosphorus oxychloride, phosphorus pentoxide, phosphorus pentachloride, phosphorus trichloride and sulfuryl chloride; dehydrating reagents such astriethylamine, chloroformate, DCC and anhydrous acetic acid.
The amount of the catalyst is usually 1 to 100 equivalents with respect to 1 equivalent of the compound [XXI].
The present invention further provides a herbicide composition comprising the tetrahydrophthalimide derivative of the present invention as effectiveingredient in an agriculturally acceptable carrier. The herbicide composition of the present invention is effective for inhibiting the growth of various weeds growing in paddy field including the weeds belonging to the Gramineae such as barnyardgrass; broadleaved weeds such as Falsepinpernel, spindle-flowered rotala, water starwart and monochoria;and those belonging to the family cyperaceae such as small flower umbrellaplant, slender spikerush and water nutgrass. Further, the tetrahydrophthalimide derivative of the present invention is particularly effective for inhibiting the growth of weeds growing in fields, such as mustard, virginia pepperweed, catchweed badstraw, Kinutaso (Galium kinuta), chick weed, Common lambsquaters, nottle (Utrica Thunbergiana), Common groundsel, Alender amaranth, Cocklebur, Pale smartweed, Velvetleaf and barynard grass. The herbicide composition of the present invention does not substantially damage the crops belonging to Family Graminae such as corn, rice and wheat, so that it is highly safe.
The agriculturally acceptable carriers per se which may be employed in the present invention are well-known in the art, and either liquid carrier or solid carrier may be employed. Preferred examples of the liquid carrier ordiluent may include water, hydrocarbons, ethers, alkoxy alcohols, ketones, esters, amides and sulfoxides. Preferred examples of the solid carriers orextender may include powder and granules of inorganic materials such as slaked lime, gypsum, calcium carbonate, silica, pearlite, pumice, diatomaceous earth, alumina, zeolite and clay minerals (e.g., talc, vermiculite and kaolinite); powder and granules of plant products such as starch, cereals and glucose; and powder and granules of synthetic productssuch as phenol resins, carbon resins and vinyl chloride resins. The concentration of the active ingredient in the composition is not critical and may usually be 0.1% by weight to 90% by weight, preferably 1% by weight to 80% by weight.
If necessary, the herbicide composition of the present invention may contain a surfactant. The surfactants are well-known and widely used in the art. Preferred examples of the surfactants include anion surfactants such as alkylsulfate esters, arylsulfonic acids, salts of succinic acid and polyethyleneglycolalkylaryl ethers and ester salts of sulfuric acid; cation surfactants such as alkylamines and polyoxyethylenealkylamines; non-ionic surfactants such as polyoxyethyleneglycol ethers and polyol esters; and ampholytic surfactants. If desired, the herbicide composition of the present invention may contain other additives which are often employed in herbicide compositions. The examples of such additives may include stabilizers, dispersion stabilizers, fixing agents, effect prolongers and synergists. The composition may also contain other herbicides, bacteriocides, fungicides and the like.
The herbicide composition may be formulated to an emulsifiable concentrate,wettable powder, aqueous solution, oily solution, granule or powder. The methods of formulating herbicide composition are well-known in the art.
Specific non-limiting examples of the preferred formulations of the presentinvention will now be described. In the following examples, all parts are based on weight.
______________________________________
Formulation 1 (Emulsifiable Concentrate)
______________________________________
Compound of the present invention:
20 parts
xylene: 60 parts
Solpol (a surfactant commercially
20 parts
available from Toho Kogaku Kogyo)
______________________________________
This formulation may be prepared by uniformly mixing the components.
______________________________________
Formulation 2 (Wettable Powder)
______________________________________
Compound of the present invention
20 parts
White Carbon 10 parts
Zeaklite 65 parts
Solpol (a surfactant commercially
5 parts
available from Toho Kogaku Kogyo)
______________________________________
This composition may be prepared by mixing and pulverizing the components.
______________________________________
Formulation 3 (Wettable Powder)
______________________________________
Compound of the present invention
10 parts
Zeaklite 87 parts
Neoplex Powder (commercially
1.5 parts
available from Kao corporation)
Solpol (a surfactant commercially
1.5 parts
available from Toho Kogaku Kogyo)
______________________________________
This composition may be prepared by mixing and pulverizing the components.
The amount of the compound of the present invention to be applied to the field varies depending on the formulation of the composition, method of application, species and stage of growth of the weeds. Typically, the amount to be applied may be 0.05 kg/ha to 10 kg/ha, preferably 0.1 kg/ha to 5 kg/ha in terms of the weight of the active compound of the present invention.
The herbicide composition of the present invention may directly be applied to the leaves or stems of weeds or to the field before the germination of the weeds. The herbicide composition may be applied as it is or may be diluted with water before use.
The invention will now be described by way of the examples thereof. It should be understood that the examples are presented for the illustration purpose only and should not be interpreted any restrictive way.
To 20 ml of acetonitrile containing 0.59 g of N-(4-chloro-2-fluoro-5-hydroxyphenyl)3,4,5,6-tetrahydrophthalimide and 0.30 g of anhydrous potassium carbonate, was added 0.30 g of 2-chloropropionic acid tetrahydrofurfuryl ester in 10 ml of acetnitrile and the resulting mixture was heated to reflux for 5 hours. After allowingto cool, water was added to the mixture and the resulting mixture was extracted with ether. After drying the extract, the solvent was evaporatedunder reduced pressure and the obtained residue was subjected to a column chromatography (silica gel) to obtain 0.65 g of oily product. The eluant employed in the column chromatography was chloroform/ethyl acetate=10/1 (v/v).
1 H-NMR (60 MHz, CDCl3 solvent) δppm 1.5-1.9 (m, 11H), 2.1-2.5 (m, 4H), 3.4-4.3 (m, 5H), 4.76 (q, J=7 Hz, 1H), 6.86 (dd, J=1.5, 6Hz, 1H), 7.28 (d, J=9 Hz, 1H)
Refractive Index (dD 25): 1.5448
The same operation as in Example 1 was repeated except that a halogen compound [VIII]](see Equation 1) having methyl groups as R1 and R2, and 3-methyl-1,2,4-oxadiazol-5-yl group as R3 was used to obtain the Compound No. 1.
1 H-NMR (60 mHz, CDCl3 solvent) δppm 1.5-2.0 (m, 10H), 2.2-2.6 (m, 7H), 4.83 (q, J=7 Hz, 1H), 6.05 (q, J=7 Hz, 1H), 6.81 (t, J=6 Hz, 1H), 7.25 (d, J=9 Hz, 1H)
Refractive Index (nD 25): 1.5382
The same operation as in Example 1 was repeated except that a halogen compound [VIII] (see Equation 1) having hydrogen as R1 and methyl group as R2, and 3-methyl-1,2,4-oxadiazol-5-yl group as R3 was used to obtain the Compound No. 2.
1 H-NMR (60 MHz, CDCl3 solvent) δppm 1.70 (d, J=7 Hz, 3H), 1.6-2.0 (m, 4H), 2.36 (s, 3H), 2.2-2.6 (m, 4H), 4.76 (s, 2H), 6.10 (q, J=7Hz, 1H), 6.83 (d, J=6 Hz, 1H), 7.25 (d, J=9 Hz, 1H)
Refractive Index (nD 25): 1.5503
The same operation as in Example 1 was repeated except that a halogen compound [VIII] (see Equation 1) having hydrogen as R1 and R2, and 3-methyl-1,2,4-oxadiazol-5-yl group as R3 was used to obtain the Compound No. 4.
1 H-NMR (60 MHz, CDCl3 solvent) δppm 1.5-1.9 (m, 4H0, 2.30 (s, 3H), 2.1-2.5 (m, 4H), 4.75 (s, 2H), 5.30 (s, 2H), 6.80 (d, J=6 Hz, 1H), 7.20 (d, J=9 Hz, 1H)
Refractive Index (nD 25): 1.5407
Field soil was packed in a plastic vat sizing 22 cm×16 cm and seeds of wheat (Triticum aestivum), corn (Zea mays) and soybean (Glycine max) were sown. The field soil was covered with soil of about 1 cm thickness which contains seeds of weeds, i.e., barnyardgrass (Echinochloa crus-galli), Velvetleaf, Slender amaranth, Cocklebur and Pale smartweed. When the barnyardgrass grew to have 2-2.5 leaves, each of the Compound Nos. 1-3 of the present invention was applied in the amount shown in Table6 below. Further, for comparison, the compound of the formula [A] disclosedin Japanese Patent Disclosure (Kokai) No. 163365/82 (comparative compound A) and the compound of the formula [B] disclosed in Japanese Patnt Disclosure (Kokai) No. 110566/83 (comparative compound B) were applied separately. After 14 days from the application of the herbicide, the conditions of the growth of the weeds and the crops were observed. The results are shown in Table 6. The herbicidal effectiveness was rated in 6ranks as follows:
Rank 0: percent growth inhibition of 0-9%
Rank 1: percent growth inhibition of 10-29%
Rank 2: percent growth inhibition of 30-49%
Rank 3: percent growth inhibition of 50-69%
Rank 4: percent growth inhibition of 70-89%
Rank 5: percent growth inhibition of 90-100%
TABLE 6
__________________________________________________________________________
Herbicidal Effectiveness
Rate Barnyard-
Pale Slender Phytotoxicity
Compound No.
(a.i. g/10a)
grass smartweed
amaranth
Cocklebur
Velvetleaf
Wheat
Corn
Soybean
__________________________________________________________________________
1 60 1 5 5 5 5 0 0 0
125 1 5 5 5 5 0 0 0
2 60 0 5 5 5 5 0 0 0
125 3 5 5 5 5 0 0 0
3 60 4 2 5 5 5 0 0 0
125 4 5 5 5 5 0 0 0
Comparative
60 2 5 5 5 5 2 2 4
Compound A
125 4 5 5 5 5 3 2 5
Comparative
60 5 5 5 5 5 0 2 2
Compound B
125 5 5 5 5 5 2 2 3
__________________________________________________________________________
To 50 ml of acetonitrile, 0.6 g of 3-methyl-5-(chloroethyl)-1,2,4-oxadiazole, 1.12 g of N-(4-chloro-2-fluoro-5-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide and 0.58 g of potassium carbonate were added and the mixture was heated to reflux for 16 hours. After the reaction mixture was allowed to cool, inorganic materials were removed by filtration and acetonitrile was evaporated. The residue was purified by column chromatography (silica gel)to obtain 0.72 g of the desired product. The eluant employed in the column chromatography was benzene/ethyl acetate=10/1 (v/v).
1 H-NMR (60 MHz, CDCl3 solvent) δppm 1.83 (d, J=7 Hz, 3H), 1.6-2.0 (m, 4H), 2.40 (s, 3H), 2.2-2.6 (m, 4H), 5.47 (q, J=7 Hz, 1H), 6.90(d, J=6 Hz, 1H) 7.24 (d, J=9 Hz, 1H)
m.p.: 95°-97.5° C.
To 50 ml of acetic acid, 1.67 g of 4-chloro-2-fluoro-5-(3-benzyl-1,2,4-oxadiazol-5-yl)methyloxyaniline and 0.76 g of 3,4,5,6-tetrahydrophthalic anhydride were added, and the mixturewas heated to reflux for 16 hours under stirring The reaction mixture was then concentrated under reduced pressure and under heat, and the residue was purified by column chromatography (silica gel) to obtain 1.73 g of thedesired product. The eluant employed in the column chromatography was benzene/ethyl acetate=10/1 (v/v).
1 H-NMR (60 MHz CDCl3 solvent) δppm 1.4-1.9 (m, 4H, 2.0-2.5(m, 4H), 4.42 (s, 2H), 5.03 (s, 2H), 5.03 (s, 2H), 6.80 (d, J=6 Hz, 1H), 6.9-7.3 (broad s, 6H)
Refractive Index (nD 25) 1.5761
The same operation as in Example 7 was repeated except that the compound [X] in Equation 2 had methyl group as R4 to obtain the Compound No. 7.
1 H-NMR (60 MHz, CDCl3 solvent δppm 1.83 (d, J=7 Hz, 3H), 1.6-2.0 (m, 4H), 2.2-2.6 (m, 4H), 4.11 (s, 2H), 5.43 (q, J=7 Hz, 1H), 6.88(d, J=6 Hz, 1H), 7.1-7.4 (m, 6H)
Refractive Index (nD 25) 1.5708
The same procedure as in Example 5 was repeated except that the compounds tested were Compound Nos. 5-7. Further, for comparison, 5-[2-chloro-4-trifluoromethyl-phenoxy]-2-nitro-benzoic acid (Comparative Compound C) and the Comparative Compound A described in Example 5 were also tested. The results are shown in Table 7 below.
TABLE 7
__________________________________________________________________________
Herbicidal Effectiveness
Rate Barnyard-
Pale Slender Phytotoxicity
Compound No.
(a.i. g/10a)
grass smartweed
amaranth
Cocklebur
Velvetleaf
Wheat
Corn
Soybean
__________________________________________________________________________
5 15 3 5 5 5 5 0 0 0
30 4 5 5 5 5 0 0 0
6 15 3 5 5 5 5 0 0 0
30 5 5 5 5 5 0 0 0
7 15 4 5 5 5 5 0 0 0
30 4 5 5 5 5 0 0 0
Comparative
15 0 5 5 4 3 0 0 3
Compound C
30 3 5 5 4.5 4.5 2 2 4
Comparative
15 0 5 4.5 4.5 5 0 0 4.5
Compound A
30 0 5 5 5 5 1 1 5
__________________________________________________________________________
To 50 ml of acetonitrile, 0.55 g of N-(4-chloro-5-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide, 0.38 g of benzyl bromide and 0.27 g of potassium carbonate were added and the mixture was heated to reflux under stirring After cooling, the inorganic materials were removed by filtration and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (silica gel, benzene/ethyl acetate=10/1 (v/v)) to obtain 0.6 g of the desired product.
Refractive Index nD 25 : 1.5909
______________________________________
Element Analysis
C H N
______________________________________
Found (%) 68.83 4.97 3.82
Calcd. (%) 68.57 4.93 3.80
______________________________________
1 H-NMR (CDCl3, δppm) 1.80 (mc, 4H), 2.40 (mc, 4H), 4.92 (s, 2H), 7.20 (mc, 8H)
To 50 ml of acetic acid, 0.43 g of 3,4,5,6-tetrahydrophthalic anhydride and0.80 g of 2,4-dichloro-5-aminophenyl-2'-fluorobenzyl ether were added and the mixture was heated to reflux for 16 hours under stirring. After cooling, the solvent was evaporated under reduced pressure and the residuewas purified by column chromatography (silica gel, benzene/ethyl acetate=10/1 (v/v)) to obtain 0.7 g of the desired product.
m.p.: 106°-108.5° C.
______________________________________
Element Analysis
C H N
______________________________________
Found (%) 59.8 3.81 3.36
Calcd. (%) 60.01 3.83 3.33
______________________________________
1 H-NMR (CDCl3, δppm) 1.70 (mc, 4H), 2.33 (mc, 4H), 5.07 (s, 3H), 7.22 (mc, 6H)
To 50 ml of acetonitrile, 0.43 g of N-(4-chloro-5-hydroxyphenyl)-3,4,5,6-tetraphydrophthalimide, 0.3 g of 2-fluoro-benzyl bromide and 0.21 g of potassium carbonate were added and the same procedure as in Example 10 was followed to obtain 0.62 g of the Compound No. 9.
m.p.: 88.5°-91° C.
______________________________________
Element Analysis
C H N
______________________________________
Found (%) 65.71 4.27 3.31
Calcd. (%) 65.37 4.44 3.63
______________________________________
1 H-NMR (CDCl3, δppm) 1.78 (mc, 4H), 2.42 (mc, 4H), 5.10 (s, 2H), 7.20 (mc, 7H)
To 50 ml of acetonitrile, 0.55 g of N-(4-chloro-5-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide, 0.38 g of 4-fluoro-benzyl bromide and 0.27 g of potassium carbonate were added and the same procedure as in Example 10 was followed to obtain 0.7 g of the Compound No. 10.
Refractive Index nD : 1.5730
______________________________________
Element Analysis
C H N
______________________________________
Found (%) 64.99 4.52 3.98
Calcd. (%) 65.37 4.44 3.63
______________________________________
1 H-NMR (CDCl3, δppm) 1.74 (mc, 4H), 2.40 (mc, 4H), 4.92 (s, 2H), 7.10 (mc, 8H)
To 50 ml of acetonitrile, 0.46 g anhydrous N-(4-chloro-2-fluoro-5-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimidic acid,0.27 g of benzyl bromide and 0.21 g of potassium carbonate were added and the same procedure as in Example 10 was followed to obtain 0.69 g of the Compound No. 11.
Refractive Index nD 25 : 1.5968
______________________________________
Element Analysis
C H N
______________________________________
Found (%) 65.22 4.58 3.59
Calcd. (%) 65.37 4.44 3.63
______________________________________
1 H-NMR (CDCl3, δppm) 1.75 (mc, 4H), 2.38 (mc, 4H), 5.03 (s, 2H), 7.28 (mc, 7H)
To 50 ml of acetonitrile, 1.0 g of N-(4-chloro-2-fluoro-5-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide, 0.6 gof 2-fluoro-benzyl chloride and 0.56 g of potassium carbonate were added and the same procedure as in Example 10 was followed to obtain 1.02 g of the Compound No. 12.
m.p.: 93°-95° C.
______________________________________
Element Analysis
C H N
______________________________________
Found (%) 62.33 4.06 3.42
Calcd. (%) 62.46 3.99 3.46
______________________________________
1 H-NMR (CDCl3, δppm) 1.70 (mc, 4H), 2.33 (mc, 4H), 5.08 (s, 2H), 7.22 (mc, 6H)
To 50 ml of acetonitrile, 0.46 g of N-(4-chloro-2-fluoro-5-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide, 0.29 g of 2-methyl-benzyl bromide and 0.21 g of potassium carbonate were added and the same procedure as in Example 10 was followed to obtain 0.67 g of the Compound No. 13.
m.p.: 135°-137° C.
______________________________________
Element Analysis
C H N
______________________________________
Found (%) 66.12 4.67 3.2
Calcd. (%) 66.08 4.78 3.5
______________________________________
1 H-NMR (CDCl3, δppm) 1.82 (mc, 4H), 2.33 (s, 3H), 2.38 (mc, 4H), 5.17 (s, 2H), 7.13 (mc, 6H)
To 50 ml of acetonitrile, 0.75 g of N-(2-bromo-4-chloro-5-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide, 0.36 gof benzyl bromide and 0.29 g of potassium carbonate were added and the sameprocedure as in Example 10 was followed to obtain 0.57 g of the Compound No. 15.
Refractive Index: nD 25 : 1.5839
______________________________________
Element Analysis
C H N
______________________________________
Found (%) 56.55 3.7 3.23
Calcd. (%) 56.46 3.83 3.13
______________________________________
1 H-NMR (CDCl3, δppm) 1.67 (mc, 4H), 2.30 (mc, 4H), 5.03 (s, 2H), 7.17 (mc, 7H)
To 50 ml of acetic acid, 0.76 g of 3,4,5,6-tetrahydrophthalic anhydride and1.7 g of 2-bromo-4-chloro-5-aminophenyl-2'-fluorobenzyl ether were added and the same procedure as in Example 11 was followed to obtain 1.72 g of the Compound No. 16.
m.p.: 142°-144.5° C.
______________________________________
Element Analysis
C H N
______________________________________
Found (%) 54.44 3.29 2.77
Calcd. (%) 54.27 3.47 3.01
______________________________________
1 H-NMR (CDCl3, δppm) 1.70 (mc, 4H), 2.30 (mc, 4H), 5.10 (s, 2H), 7.19 (mc, 7H)
To 50 ml of acetic acid, 0.76 g of 3,4,5,6-tetrahydrophthalic anhydride and1.35 g of 4-chloro-2-fluoro-5-aminophenyl-(1-phenyl)-ethyl ether were addedand the same procedure as in Example 11 was followed to obtain 1.25 g of the Compound No. 17.
Refractive Index:nD 25 : 1.5509
______________________________________
Element Analysis
C H N
______________________________________
Found (%) 66.06 4.85 3.44
Calcd. (%) 66.08 4.78 3.5
______________________________________
1 H-NMR (CDCl3, δppm) 1.42 (d, 3H), 2.30 (mc, 4H), 2.35 (mc, 4H), 4.80 (q, 1H), 6.79 (mc, 7H)
To 50 ml of acetic acid, 0.76 g of 3,4,5,6-tetrahydrophthalic anhydride and1.92 g of 2,4-dichloro-5-aminophenyl-(1-phenyl)-ethyl ether were added and the same procedure as in Example 11 was followed to obtain 1.48 g of the Compound No. 18.
Refractive Index:nD 25 : 1.5509
______________________________________
Element Analysis
C H N
______________________________________
Found (%) 63.65 4.58 3.27
Calcd. (%) 63.47 4.6 3.36
______________________________________
1 H-NMR (CDCl3, δppm) 1.63 (d, 3H), 1.75 (mc, 4H), 2.33 (mc, 4H), 5.28 (q, 1H), 7.00 (mc, 7H)
Paddy field soil was packed in a plastic pot with 60 cm diameter. After puddling, the seeds of weeds shown in Table 8 below were sown and one seedling of rice (variety: Yamahoshi) with 2 leaves were transplanted. Thewater level was kept at about 3 cm above the soil. The herbicide compositions formulated according to the above-described Formulation 3 wasdiluted with water and was uniformly applied to the water surface in the amount shown in Table 8. Further, for comparison, N-4-chloro-2-fluoro-5-isopropoxyphenyl)2-ethoxycarbonylcyclohexyl carboxylic acid ethyl ester (Comparative Compound D) disclosed in JapanesePatent Disclosure (Kokai) No. 33154/86 was also tested. After 20 days from the application of the herbicide, the growing conditions of the weeds and the rice were observed. The growth inhibition was rated in 6 ranks as in Example 5. The results are shown in Table 8.
TABLE 8
__________________________________________________________________________
Annual
Rate Barnyard-
Small flower broadleaved
Compound No.
(a.i. g/10a)
Rice
grass unbrellaplant
Monochoria
weeds
__________________________________________________________________________
8 250 0 3 5 5 5
125 0 3 5 5 5
60 0 3 5 5 5
9 250 0 0 5 5 5
125 0 0 5 5 5
60 0 0 5 5 5
10 250 0 0 4 5 5
125 0 0 4 5 5
60 0 0 3 5 5
11 125 1 5 5 5 5
60 0 5 5 5 5
30 0 5 5 5 5
12 125 0 5 5 5 5
60 0 5 5 5 5
30 0 5 5 5 5
13 125 0 4 5 5 5
60 0 4 5 5 5
30 0 4 5 5 5
14 250 0 2 5 5 5
125 0 0 5 4 5
60 0 0 4 4 5
15 125 0 4 5 5 5
60 0 4 5 5 5
30 0 4 5 5 5
16 250 0 4 5 5 5
125 0 4 5 4 5
60 0 3 5 4 5
17 125 0 5 5 5 5
60 0 5 5 5 5
30 0 4 5 5 5
18 125 0 4 5 5 5
60 0 3 5 5 5
30 0 3 5 5 5
Comparative
125 0 0 2 0 0
Compound D
60 0 0 0 0 0
30 0 0 0 0 0
__________________________________________________________________________
The same procedure as in Example 5 was repeated except that the compounds tested were Compound Nos. 11-18. Further, for comparison, the Comparative Compound D described in Example 21 was also tested. The results are shown in Table 9 below.
TABLE 9
__________________________________________________________________________
Rate Slender
Compound No.
(a.i. g/10a)
Soybean
Wheat
Corn
amaranth
Velvetleaf
Cocklebur
__________________________________________________________________________
11 125 1 0 1 5 5 5
60 1 0 0 5 5 5
30 0 0 0 5 5 5
12 125 1 0 0 5 5 5
60 0 0 0 5 5 5
30 0 0 0 5 5 4.5
13 125 1 0 1 5 5 4.5
60 0 0 0 5 4.5 4
30 0 0 0 5 4.5 3
15 125 2 0 0 5 5 4.5
60 1 0 0 5 4.5 3
30 1 0 0 5 4.5 3
16 125 1 0 0 4 4 3
60 0 0 0 4 3 3
30 0 0 0 3 3 0
17 125 3 2 1 5 5 5
60 3 2 1 5 5 5
30 2 1 0 5 5 4.5
18 125 1 0 0 5 5 4
60 1 0 0 5 5 4
30 1 0 0 3 5 4
Comparative
125 0 0 0 0 1 0
Compound D
60 0 0 0 0 0 0
30 0 0 0 0 0 0
__________________________________________________________________________
To 50 ml of acetic acid, 3.19 g of 3,4,5,6-tetrahydrophthalic anhydride and4.95 g of 2-(2,4-dichloro-5-aminophenoxy)propanol were added and the mixture was heated to reflux under stirring for 16 hours. After cooling, the solvent was evaporated under reduced pressure and the residue was purified by column chromatography (silica gel, benzene/ethyl acetate=10/1 (v/v)) to obtain 1.42 g of the desired product.
Refractive Index: nD 25 1.5640
1 H-NMR (CDCl3, δppm) 1.22 (3H, d), 1.43-1.92 (4H, m), 2.09-2.72 (4H, m), 3.65 (2H, d), 4.20 (1H, m), 4.37 (1H, br), 6.87 (1H, s), 7.42 (1H, s)
The same procedure as in Example 23 was repeated except that 2-(2-chloro-4-fluoro 5-aminophenoxy)propanol was used as the aniline derivative to obtain the desired product.
Refractive Index: nD 25 1.5494
1 H-NMR (CDCl3, δppm) 1.25 (3H, d), 1.47-1.94 (4H, m), 2.11-2.67 (4H, m), 3.69 (2H, d), 3.85 (1H, m), 4.33 (1H, br), 6.89 (1H, s), 7.17 (1H, s)
The same procedure as in Example 23 was repeated except that O-acetyl derivative of 2-(2-chloro-4-fluoro-5-aminophenoxy)propanol was used as theaniline derivative to obtain the desired product.
Refractive Index: nD 1.5410
1 H-NMR (CDCl3, δppm) 1.30 (3H, d), 1.50-1.95 (4H, m), 1.99(3H, s), 2.17-2.63 (4H, m), 4.21 (2H, d), 4.50 (1H, br), 6.90 (1H, s), 7.18(1H, s)
The same procedure as in Example 23 was repeated except that 4-chloro-2-fluoro-5-(2-(1-benzyloxypropyl)oxyaniline was used as the aniline derivative to obtain the desired
Refractive Index: nD 25 1.5508
1 H-NMR (CDCl3, δppm) 1.28 (3H, d), 1.64-1.97 (4H, m), 2.23-2.62 (4H, m), 4.40 (2H, m), 4.50 (1H, s), 6.82-7.48 (7H, m)
The same procedure as in Example 23 was repeated except that 2,4-dichloro-5-(2-(1-o-fluorobenzyloxypropyl)oxy)aniline was used as the aniline derivative to obtain the desired product.
Refractive Index: nD 25 1.5668
1 H-NMR (CDCl3, δppm) 1.42 (3H, d), 1.55-2.08 (4H, m), 2.17-2.70 (4H, m), 4.58 (2H, m), 4.70 (1H, m), 6.70-7.58 (6H, m)
The same procedure as in Example 21 was repeated except that the compounds tested were Compound No.s 19-23. For comparison, the Comparative Compound D described in Example 21 was also tested. The results are shown in Table 10 below.
TABLE 10
__________________________________________________________________________
Herbicidal Effectiveness
Rate Barnyard-
Pale Slender Phytotoxicity
Compound No.
(a.i. g/10a)
grass smartweed
amaranth
Velvetleaf
Cocklebur
Soybean
Wheat
Corn
__________________________________________________________________________
19 30 5 5 5 5 5 2 0 0
15 4 5 5 5 5 2 0 0
20 30 5 5 5 5 5 3 0 0
15 5 5 5 5 5 3 0 0
21 30 5 5 5 5 4 3 0 0
15 5 5 5 4 3 3 0 0
22 60 0 3 5 5 5 1 0 0
30 0 3 5 5 4 1 0 0
23 60 0 4 5 5 5 1 0 0
30 0 4 5 5 4 1 0 0
Comparative
60 1 3 4 3 4 2 0 0
Compound D
30 0 2 3 3 3 1 0 0
__________________________________________________________________________
The same procedure as in Example 5 was repeated except that the compounds tested were Compound Nos. 19-23. Further, for comparison, the Comparative Compound D described in Example 21 was also tested. The results are shown in Table 11 below.
TABLE 11
__________________________________________________________________________
Herbicidal Effectiveness
Annual
Rate Barnyard-
Small flower broadleaved
Phytotoxicity
Compound No.
(a.i. g/10a)
grass umbrellaplant
Bulrush
Monochoria
weeds Rice
__________________________________________________________________________
19 30 5 5 4 5 5 1
15 5 5 3 5 5 1
20 30 4 5 3 5 5 1
15 4 5 3 5 5 1
21 30 4 5 3 5 5 1
15 4 5 3 5 5 1
22 60 5 5 0 5 5 0
30 4 4 0 5 5 0
23 60 5 5 3 5 5 0
30 5 4 3 5 5 0
Comparative
60 4 5 4 5 5 3
Compound D
30 3 5 3 4 5 2
__________________________________________________________________________
To 50 ml of acetic acid, 2.47 g of 3,4,5,6-tetrahydrophthalic anhydride and2.56 g of 4-chloro-5-hydroxymethyl aniline were added and the mixture was heated to reflux under stirring for 16 hours. After cooling, the solvent was evaporated under reduced pressure and the residue was purified by column chromatography (silica gel, benzene/ethyl acetate=10/1 (v/v)) to obtain 1.82 g of the desired product.
m.p.: 77°-79° C.
1 H-NMR (CDCl3, δppm) 1.52-1.98 (4H, m), 2.18-2.61 (4H, m),3.08 (1H, s), 4.72 (2H, s), 6.95-7.57 (3H, m)
To 30 ml of thionyl chloride, 1.13 g of N-(2-fluoro-4-chloro-5-aminocarbonylphenyl)-3,4,5,6-tetrahydrophthalimide was added and the mixture was heated to reflux under stirring for 16 hours. After cooling, the solvent was evaporated under reduced pressure and the residue was purified by column chromatography (silica gel, benzene/ethyl acetate=10/1 (v/v)) to obtain 0.63 g of the desired product.m.p.: 160°-162° C.
1 H-NMR (CDCl3, δppm) 1.67-2.10 (4H, m), 2.20-2.70 (4H, m),7.40 (1H, d), 7.60 (1H, d)
The same procedure as in Example 30 was repeated except that 4-chloro-5-((acetyloxy)methyl]aniline was used as the aniline derivative to obtain the Compound No. 25.
m.p.: 100°-101° C.
1 H-NMR (CDCl3, δppm) 1.52-2.03 (4H, m), 2.13 (3H, s), 2.22-2.72 (4H, m), 5.22 (2H, s), 7.03-7.58 (3H, m)
The same procedure as in Example 30 was repeated except that 4-chloro-5-[[1-(ethoxycarbonyl)ethoxy)methyl]aniline was used as the aniline derivative to obtain the Compound No. 26.
m.p.: 77°-79° C.
1 H-NMR (CDCl3, δppm) 1.50-1.96 (4H, m), 2.17-2.65 (4H, m),4.72 (4H, s), 6.78-7.67 (7H, m)
The same procedure as in Example 30 was repeated except that 4-chloro-5-[[1-(ethoxycarbonyl)ethoxy]methyl]aniline was used as the aniline derivative to obtain the Compound No. 27.
Refractive Index: nD 25 1.5512
1 H-NMR (CDCl3, δppm) 1.42 (3H, t), 1.62-2.07 (4H, m), 2.15-2.65 (4H, m), 4.22 (4H, q), 4.70 (2H, s), 7.00-7.63 (3H, m)
The same procedure as in Example 31 was repeated except that N-(4-chloro-5-aminocarbonylphenyl)-3,4,5,6-tetrahydrophthalimide was used to obtain the Compound No. 28.
m.p.:135°-137° C.
1 H-NMR (CDCl3, δppm) 1.58-2.03 (4H, m), 2.15-2.72 (4H, m),7.27-7.83 (3H, m)
The same procedure as in Example 31 was repeated except that N-(4-bromo-5-aminocarbonylphenyl)-3,4,5,6-tetrahydrophthalimide was used to obtain the Compound No. 29.
m.p.:151°-153° C.
1 H-NMR (CDCl3, δppm) 1.62-2.11, (4H, m), 2.18-2.76 (4H, m), 7.37-7.93 (3H, m)
The same procedure as in Example 31 was repeated except that N-(4-trifluoromethyl-5-aminocarbonylphenyl)-3,4,5,6-tetrahydrophthalimide was used to obtain the Compound No. 31.
m.p.: 211°-214° C.
1 H-NMR (CDCl3, δppm) 1.58-2.05 (4H, m), 2.23-2.80 (4H, m),7.57-8.07 (3H, m)
The same procedure as in Example 21 was repeated except that the compounds tested were Compound Nos. 24-30. For comparison, the Comparative Compound A described in Example 5 was also tested. The results are shown in Table 12 below.
TABLE 12
__________________________________________________________________________
Herbicidal Effectiveness
Annual
Rate Small flower broadleaved
Phytotoxicity
Compound No.
(a.i. g/10a)
umbrellaplant
Monochoria
weeds Rice
__________________________________________________________________________
24 60 5 5 5 0
30 4 5 5 0
25 125 5 5 5 0
60 5 4 5 0
26 30 5 5 3 0
15 5 5 3 0
27 125 4 5 5 0
60 4 4 4 0
28 30 5 5 5 0
15 5 5 5 0
29 30 5 5 5 0
15 5 5 5 0
Comparative
60 5 5 5 3
Compound A
30 5 4 5 2
__________________________________________________________________________
The same procedure as in Example 5 was repeated except that the compounds tested were Compound Nos. 24, 25, 27-31. Further, for comparison, the Comparative Compound A described in Example 5 was also tested. The resultsare shown in Table 13 below.
TABLE 13
__________________________________________________________________________
Herbicidal Effectiveness
Rate Pale Slender Phytotoxicity
Compound No.
(a.i g/10a)
smartweed
amaranth
Velvetleaf
Cocklebur
Soybean
Wheat
Corn
__________________________________________________________________________
24 60 3 5 5 5 1 0 0
30 3 5 5 4 1 0 0
25 60 3 5 5 4 0 0 0
30 3 4 5 4 0 0 0
27 30 5 5 5 5 2 0 0
15 5 5 5 5 1 0 0
28 60 4 5 5 5 1 0 0
30 4 5 5 4 1 0 0
29 125 3 5 5 4 0 0 0
60 3 5 5 4 0 0 0
30 30 5 5 5 5 1 0 0
15 5 5 5 5 1 0 0
31 30 5 5 5 5 2 1 0
15 5 5 5 5 2 0 0
Comparative
60 3 4 3 4 2 0 0
Compound A
30 2 3 3 3 1 0 0
__________________________________________________________________________
Claims (8)
1. A tetrahydrophthalimide derivative of the formula (I): ##STR30## wherein X1 is fluorine and X2 represents halogen, hydrogen or trifluoromethyl; R represents: ##STR31## wherein R1 and R2, which may be the same or different, represent hydrogen or methyl, R3 represents 2-tetrahydrofurfuryl or 3-methyl-1,2,4-oxadizol-5-yl; ##STR32## wherein R4 is hydrogen or methyl, R5 is methyl or benzyl; ##STR33## wherein R8 is hydrogen, acyl or arylalkyl, or a C1 -C4 alkyl substituted with an alkoxycarbonyl group.
2. The tetrahydrophthalimide derivative of claim 1, which is represented by the formula: ##STR34## wherein R1, R2 and R3 represent the same meaning as in claim 1.
3. The tetrahydrophthalimide derivative of claim 1, which is represented by the formula: ##STR35## wherein R4 and R5 represent the same meaning as in claim 1.
4. The tetrahydrophthalimide derivative of claim 1, which is represented by the formula: ##STR36## wherein X3 and X4, the same or different, represent halogen, R8 represent the same meaning as in claim 1.
5. A herbicide composition comprising a herbicidal effective amount of the tetrahydrophthalimide derivative of claim 1 in an agriculturally acceptable carrier.
6. The herbicide composition of claim 5, which comprises a herbicidal effective amount of the tetrahydrophthalimide derivative of claim 2 in an agriculturally acceptable carrier.
7. The herbicide composition of claim 5, which comprises a herbicidal effective amount of the tetrahydrophthalimide derivative of claim 3 in an agriculturally acceptable carrier.
8. The herbicide composition of claim 5, which comprises a herbicidal effective amount of the tetrahydrophthalimide derivative of claim 5 in an agriculturally acceptable carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/726,724 US5169428A (en) | 1987-12-30 | 1991-07-01 | Tetrahydrophthalimide derivative and herbicide composition containing same |
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62334000A JP2542885B2 (en) | 1987-12-30 | 1987-12-30 | N-phenyltetrahydrophthalimide derivative, method for producing the same, and herbicide containing the same as an active ingredient |
| JP62-334000 | 1987-12-30 | ||
| JP62336451A JP2542886B2 (en) | 1987-12-31 | 1987-12-31 | Tetrahydrophthalimide derivative and herbicide containing it as an active ingredient |
| JP62-336451 | 1987-12-31 | ||
| JP63-225465 | 1988-09-08 | ||
| JP63-225463 | 1988-09-08 | ||
| JP63225465A JPH0273066A (en) | 1988-09-08 | 1988-09-08 | Tetrahydrophthalimide derivative and herbicide containing said derivative as active ingredient |
| JP63225463A JPH0273064A (en) | 1988-09-08 | 1988-09-08 | Tetrahydrophalimide derivative and herbicide containing said derivative as active ingredient |
| JP63-234258 | 1988-09-19 | ||
| JP63234258A JPH0283368A (en) | 1988-09-19 | 1988-09-19 | Tetrahydrophthalimide derivative and herbicide containing the same derivative as active ingredient |
| US29175989A | 1989-12-29 | 1989-12-29 | |
| US07/726,724 US5169428A (en) | 1987-12-30 | 1991-07-01 | Tetrahydrophthalimide derivative and herbicide composition containing same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US29175989A Continuation | 1987-12-30 | 1989-12-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5169428A true US5169428A (en) | 1992-12-08 |
Family
ID=27566619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/726,724 Expired - Fee Related US5169428A (en) | 1987-12-30 | 1991-07-01 | Tetrahydrophthalimide derivative and herbicide composition containing same |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US5169428A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20240300932A1 (en) * | 2023-02-23 | 2024-09-12 | Guizhou University | N-phenylimine derivative and preparation method and use thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2119703A5 (en) * | 1970-12-23 | 1972-08-04 | Mitsubishi Chem Ind | |
| DE3013162A1 (en) * | 1979-04-13 | 1980-10-30 | Mitsubishi Chem Ind | N-SUBSTITUTED TETRAHYDROPHTHALIMIDES AND HERBICIDES WITH A CONTENT THE SAME |
| EP0049508A1 (en) * | 1980-10-07 | 1982-04-14 | Mitsubishi Kasei Corporation | N-(3-Substituted oxyphenyl) tetrahydrophthalimides and herbicidal composition |
| EP0061741A2 (en) * | 1981-03-30 | 1982-10-06 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimides, and their production and use |
| EP0068822A2 (en) * | 1981-06-29 | 1983-01-05 | Rohm And Haas Company | Novel heterocyclic substituted benzenes, herbicidal compositions containing them and the use thereof for combating weeds |
| EP0083055A2 (en) * | 1981-12-25 | 1983-07-06 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimide compounds, and their production and use |
| US4431822A (en) * | 1981-03-30 | 1984-02-14 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimides, and their production and use |
| US4484940A (en) * | 1981-09-01 | 1984-11-27 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimides, and their production and use as herbicides |
| US4484941A (en) * | 1981-09-01 | 1984-11-27 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimides, and their production and use as herbicides |
| EP0150064A2 (en) * | 1984-01-21 | 1985-07-31 | Sumitomo Chemical Company, Limited | 3-Amino-4-fluorophenylethers and their production |
| WO1987004049A1 (en) * | 1986-01-10 | 1987-07-16 | Fmc Corporation | N-substituted tetrahydrophthalimide herbicidal compounds and intermediates therefor |
| WO1987007602A2 (en) * | 1986-06-03 | 1987-12-17 | Rhone-Poulenc Agrochimie | N-(5-substituted methylene) phenyl herbicides |
| USH531H (en) * | 1986-06-03 | 1988-10-04 | Anilide herbicide derivatives |
-
1991
- 1991-07-01 US US07/726,724 patent/US5169428A/en not_active Expired - Fee Related
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2119703A5 (en) * | 1970-12-23 | 1972-08-04 | Mitsubishi Chem Ind | |
| DE3013162A1 (en) * | 1979-04-13 | 1980-10-30 | Mitsubishi Chem Ind | N-SUBSTITUTED TETRAHYDROPHTHALIMIDES AND HERBICIDES WITH A CONTENT THE SAME |
| EP0049508A1 (en) * | 1980-10-07 | 1982-04-14 | Mitsubishi Kasei Corporation | N-(3-Substituted oxyphenyl) tetrahydrophthalimides and herbicidal composition |
| US4431822A (en) * | 1981-03-30 | 1984-02-14 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimides, and their production and use |
| EP0061741A2 (en) * | 1981-03-30 | 1982-10-06 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimides, and their production and use |
| EP0068822A2 (en) * | 1981-06-29 | 1983-01-05 | Rohm And Haas Company | Novel heterocyclic substituted benzenes, herbicidal compositions containing them and the use thereof for combating weeds |
| US4484940A (en) * | 1981-09-01 | 1984-11-27 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimides, and their production and use as herbicides |
| US4484941A (en) * | 1981-09-01 | 1984-11-27 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimides, and their production and use as herbicides |
| EP0083055A2 (en) * | 1981-12-25 | 1983-07-06 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimide compounds, and their production and use |
| EP0172306A1 (en) * | 1981-12-25 | 1986-02-26 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimide compounds, their production and use |
| US4670046A (en) * | 1981-12-25 | 1987-06-02 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimide compounds, as post-emergence herbicides for use in soybean fields |
| EP0150064A2 (en) * | 1984-01-21 | 1985-07-31 | Sumitomo Chemical Company, Limited | 3-Amino-4-fluorophenylethers and their production |
| WO1987004049A1 (en) * | 1986-01-10 | 1987-07-16 | Fmc Corporation | N-substituted tetrahydrophthalimide herbicidal compounds and intermediates therefor |
| WO1987007602A2 (en) * | 1986-06-03 | 1987-12-17 | Rhone-Poulenc Agrochimie | N-(5-substituted methylene) phenyl herbicides |
| USH531H (en) * | 1986-06-03 | 1988-10-04 | Anilide herbicide derivatives |
Non-Patent Citations (3)
| Title |
|---|
| Chemical Abstracts, vol. 101, No. 19, Nov. 5, 1984, p. 687, column 1, Abstract No. 171089u. * |
| Chemical Abstracts, vol. 102, No. 9, Mar. 4, 1985, p. 584, column 1, Abstract No. 78702d. * |
| Chemical Abstracts, vol. 97, No. 25, Dec. 20, 1982, p. 834, column 2, Abstract No. 215986q. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20240300932A1 (en) * | 2023-02-23 | 2024-09-12 | Guizhou University | N-phenylimine derivative and preparation method and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4826533A (en) | N-(substituted phenyl)-tetrahydrophthalimide compounds, and their production and herbicide use | |
| EP0104532B1 (en) | O-halobenzoic acid derivatives, process for their preparation, herbicidal compositions and their use | |
| US4948421A (en) | Phenoxypropionic acid ester derivatives as herbicides | |
| EP1681287A1 (en) | Benzoxazole compounds, process for producing the same, and herbicides | |
| US4406688A (en) | Herbicidal 4-benzoyl-5-phenacyloxy-pyrazole derivatives, composition and method | |
| EP0493606B1 (en) | Heterocycle-substituted benzene derivative, production thereof, and herbicide containing the same as active ingredient | |
| US5169428A (en) | Tetrahydrophthalimide derivative and herbicide composition containing same | |
| CS226733B2 (en) | Herbicide and method of preparing active component thereof | |
| US5292922A (en) | N-acyl-N-phenyltetrahydrophthalamic acid derivatives, methods of producing same, and herbicides containing same as effective components | |
| EP0796845B1 (en) | Arylheterocycles with herbicidal activity | |
| US5068365A (en) | Hexahydrophthalic anilide derivatives | |
| CA1110651A (en) | Phenoxy-phenoxy-alkane-carboxylic acid derivatives | |
| US4753671A (en) | 1,2,4-oxadiazole derivatives, and selective herbicidal compositions containing them | |
| US6706664B1 (en) | Benzoxazole compounds, process for the preparation thereof and herbicides | |
| JP2810544B2 (en) | N-acyl-N-phenyltetrahydrophthalamic acid derivative, method for producing the same, and herbicide containing the same as an active ingredient | |
| EP0323271A1 (en) | Tetrahydrophthalimide derivative and herbicide composition containing the same | |
| US6337417B1 (en) | N-phenyltetrahydrophthalamic acid derivatives, methods of producing same, and herbicides containing same as effective components | |
| US5481022A (en) | N-aryloxyacyl-n-phenyltetrahydrophthalamic acid derivatives, methods of producing same, and herbicides containing same as effective components | |
| US5468719A (en) | N-acyl-n-phenyltetrahydrophthalamic acid derivatives, methods of producing same, and herbicides containing same as effective components | |
| US5207819A (en) | Phenoxypropionic acid ester derivatives | |
| US5510317A (en) | N-acyl-N-phenylmaleamic acid derivatives, methods of producing same, and herbicides containing same as effective components | |
| EP0073409A1 (en) | N-substituted-tetrahydroisophthalimide derivatives | |
| US4498922A (en) | N-aminomethylhaloacetanilides and their use for controlling undesirable plant growth | |
| JP2542886B2 (en) | Tetrahydrophthalimide derivative and herbicide containing it as an active ingredient | |
| JP2726404B2 (en) | Substituted phenyl carbonate derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| REMI | Maintenance fee reminder mailed | ||
| LAPS | Lapse for failure to pay maintenance fees | ||
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19961211 |
|
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |